Water stable compositions and articles comprising starch and methods of making the same

ABSTRACT

Thermoplastic polymer compositions comprising starch and articles made therefrom are water stable or may be rendered so. One method of making water stable thermoplastic compositions comprises the steps of mixing destructured starch with polyhydric alcohol and acid, and forming an ester condensation reaction product from at least a portion of the polyhydric alcohol and acid. In some embodiments, a pre-polymer formed from the ester condensation reaction may be provided as a pre-polymer that is mixed with the starch.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation of prior U.S. application Ser. No.11/545,263 filed on Oct. 10, 2006; which claims the benefit of U.S.Provisional Application No. 60/725,424, filed 11 Oct., 2005.

FIELD OF THE INVENTION

The present invention relates to thermoplastic polymer compositionscomprising starch and articles made therefrom. The compositions andarticles are water stable, or may be rendered so. The invention alsorelates to methods of making the water stable thermoplastic polymercompositions and articles.

BACKGROUND OF THE INVENTION

Thermoplastic polymers find use in a variety of plastic articlesincluding, but not limited to films, sheets, adhesives, binders,laminates, coatings, fibers, foams, molded articles, and the like.Often, the plastic articles have a short use cycle, as in the areas ofpackaging, agriculture, household goods, and personal care products. Forexample, in the packaging of food, plastic articles often play the roleof a protective agent and are quickly disposed of after the food isconsumed. Likewise, plastic household articles such as detergentbottles, and plastic personal care products such as diapers and tamponapplicators, are discarded upon use.

Typically, plastic articles are made from petroleum-based thermoplasticpolymers including, but not limited to, polyolefins. However, the use ofpetroleum-based thermoplastic polymers is becoming less pragmatic due todisruptions in petroleum supply and increasing expense. Additionally,after use it is common for petroleum-based plastic materials, which aretypically not biodegradable, to become solid waste that is to bediscarded in rapidly vanishing, increasingly expensive landfill space.

Thermoplastic starch (TPS) has been identified as a substitute forpetroleum-based polymers. The use of TPS is advantageous since starch isnaturally abundant, and relatively inexpensive. Moreover, TPS hasdesirable properties not typically observed in conventionalpetroleum-based polymers including, but not limited to,biodegradability, natural hydrophilicity and compatibility withmaterials traditionally incompatible with petroleum-based polymers.

To render starch thermoplastic for processing, it is typically combinedwith one or more plasticizers and/or other processing aids. Like manypetroleum-based polymers, TPS may be processed using conventional meansincluding, but not limited to, melt spinning and other melt extrusiontechniques. However, unlike many petroleum-based polymers, TPS issusceptible to moisture. When exposed to water, TPS can partially oreven fully disintegrate within hours. This susceptibility to moisturecan limit the applications in which TPS may be utilized. One proposedsolution to overcome the susceptibility of TPS to water is to blend itwith petroleum-based polymers including, but not limited to,polyolefins. However, the addition of petroleum-based polymers to TPSmay propagate disadvantages such as those described above.

There remains a need for water stable thermoplastic polymer compositionsmade from abundant, low-cost starch. The thermoplastic polymercompositions would advantageously be water stable without requiring theuse of additives including, but not limited to, petroleum products andthe like.

A further need remains for water stable plastic articles comprising TPScompositions, which may optionally be biodegradable. It would also beadvantageous for such articles to be water stable without requiring theuse of additives including, but not limited to, petroleum based productsand the like.

It is also desirable to provide starch compositions that may beconverted into water stable thermoplastic polymer compositions. Plasticarticles made from such compositions could be rendered water stableduring or after processing. Additionally, it is desirable to provide thestarch compositions, and/or components thereof, in forms that are easyto make, ship, process, and combinations thereof.

SUMMARY OF THE INVENTION

In some embodiments, the present invention relates to water stablethermoplastic polymer compositions comprising destructured starch, andester condensation reaction products formed from a reaction mixturecomprising polyhydric alcohol and acid. In some embodiments, thecomposition comprises destructured starch and reaction products ofpolyhydric alcohol and a compound, wherein the reaction products aretransesterification reaction products, ester condensation reactionproducts, and combinations thereof.

Plastic articles that may be made from the disclosed water stablethermoplastic polymer compositions include, but are not limited tomolded articles, extruded articles, and combinations thereof. Specificembodiments include personal hygiene articles, absorbent articles, andpackaging.

In some embodiments, the present invention relates to starchcompositions which may be converted to water stable thermoplasticpolymer compositions. These compositions comprise starch (which isdestructured before addition to the composition and/or in situ),polyhydric alcohol, acid and optionally triglyceride. Methods aredisclosed by which the starch compositions may be rendered water stable;the method steps may be performed in any suitable order. The methodsinclude inducing ester condensation reactions between polyhydric alcoholand acid and/or inducing transesterification reactions between thepolyhydric alcohol and triglyceride. In some embodiments, thereaction(s) are induced through the addition of heat.

These and other embodiments, aspects, and advantages are encompassedwithin the present invention, and will become better understood withregard to the following description and appended claims.

DETAILED DESCRIPTION OF THE INVENTION

All percentages, ratios and proportions used herein are by weightpercent of the composition, unless otherwise specified. All averagevalues are calculated “by weight” of the composition or componentsthereof, unless otherwise expressly indicated. “Average molecularweight,” or “molecular weight” for polymers, unless otherwise indicated,refers to weight average molecular weight. Weight average molecularweight, unless otherwise specified, is determined by gel permeationchromatography.

“Copolymer” as used herein is meant to encompass copolymers,terpolymers, and other multiple-monomer polymers.

“Reactant” as used herein refers to a chemical substance that is presentat the start of a chemical reaction.

“Mixture” as used herein refers to a mixture of two or more of any of adefined group of components, unless otherwise specified.

“Biodegradable” as used herein refers to the ability of a compound toultimately be degraded completely into CH₄, CO₂ and water or biomass bymicroorganisms and/or natural environmental factors.

“Compostable” as used herein refers to a material that meets thefollowing three requirements: (1) the material is capable of beingprocessed in a composting facility for solid waste; (2) if so processed,the material will end up in the final compost; and (3) if the compost isused in the soil, the material will ultimately biodegrade in the soil.

“Comprising” as used herein means that various components, ingredientsor steps can be conjointly employed in practicing the present invention.Accordingly, the term “comprising” encompasses the more restrictiveterms “consisting essentially of” and “consisting of”. The presentcompositions can comprise, consist essentially of, or consist of any ofthe required and optional elements disclosed herein.

Markush language as used herein encompasses combinations of theindividual Markush group members, unless otherwise indicated.

All percentages, ratios and proportions used herein are by weightpercent of the composition, unless otherwise specified. All averagevalues are calculated “by weight” of the composition or componentsthereof, unless otherwise expressly indicated.

All numerical ranges disclosed herein, are meant to encompass eachindividual number within the range and to encompass any combination ofthe disclosed upper and lower limits of the ranges.

The present invention is directed to starch compositions, as well asthermoplastic polymer compositions comprising starch and plasticarticles made therefrom, which are, or may be rendered, water stable.The present invention is also directed to methods of making the same.

The water stable thermoplastic polymer compositions of the presentinvention are made from mixtures of materials also referred to herein as“starch compositions”. The starch compositions may comprise:destructured starch; polyhydric alcohol; and acid (comprising carboxylicacid, and/or carboxylic acid anhydride moieties) and/or triglyceride,and the like. Without wishing to be bound by theory, it is believed thatthe polyhydric alcohol acts as a plasticizer which makes destructuredstarch thermoplastic and capable of being processed via methodsincluding, but not limited to, those that are used for processingconventional thermoplastics. It is further believed that by heating themixture of materials, an ester condensation reaction is induced betweenat least a portion of the polyhydric alcohol and the acid, and/or atransesterification reaction is induced between at least a portion ofthe polyhydric alcohol and triglyceride. It is believed that thesereactions, either alone or in combination, make at least a portion ofthe polyhydric alcohol water insoluble. It is believed that the waterinsoluble polyhydric alcohol may provide the resulting thermoplasticpolymer compositions (or articles made therefrom) with “waterstability”. “Water stability” generally refers to the ability towithstand moisture and is measured as specified in the Methods sectionbelow. Thus, thermoplastic compositions comprising starch of the presentinvention may be water stable without requiring the use of petroleumbased polymers and the like.

In some embodiments, the polyhydric alcohol and the acid and/ortriglyceride may be present in the starch compositions as what is termedherein as a “pre-polymer”. In these instances, the aforementionedcondensation reaction and/or transesterification reaction has already atleast partially, but not completely, taken place between the polyhydricalcohol and the acid and/or triglyceride before it is mixed with thestarch. In further embodiments, the pre-polymer may also contain starch.

The aforementioned materials, articles and methods of making the sameare further discussed below.

Starch

Starch is naturally abundant and can be relatively inexpensive.Thermoplastic starch can have desirable properties not typicallyobserved in conventional petroleum-based polymers including, but notlimited to, biodegradability, compostability, natural hydrophilicity andcompatibility with materials traditionally incompatible withpetroleum-based polymers.

Starch may take several different forms. As used herein, “native starch”means starch as it is found in its naturally occurring, unmodified form.Any suitable source of native starch is of use in the present invention.Non-limiting examples of sources include: corn starch, potato starch,sweet potato starch, wheat starch, sago palm starch, tapioca starch,rice starch, soybean starch, arrow root starch, bracken starch, lotusstarch, cassaya starch, waxy maize starch, high amylase corn starch,commercial amylase powder, and combinations thereof.

Native starch generally has a granular structure. In order to renderstarch capable of further processing, it is typically subject to adestructuring process. Without wishing to be bound by theory, it isbelieved that a starch granule is comprised of discrete amylopectin andamylase regions. To convert native starch to “destructured starch”, theregions are broken apart during the destructurization process, which isoften followed by a volume expansion of the starch, particularly in thepresence of additives including, but not limited to, plasticizer. Thepresence of a plasticizer, such as polyhydric alcohol, when starch isdestructured typically increases the starch's viscosity as compared tostarch that is destructured in its absence. The destructuring process istypically irreversible. In some embodiments of the present invention, itmay be desirable to destructure the starch as fully as possible, so asto avoid “lumps” which may have an adverse impact in subsequentprocessing steps including, but not limited to melt processing.

Native starch of use in the present invention may be destructured priorto its inclusion in the mixtures of present invention. In addition, orin the alternative, native starch may be destructured after it is in themixture, i.e., in situ. In some embodiments of the present invention,the use of native starch is less expensive than using destructuredstarch, as it eliminates the use of a separate, destructuring step.

Native starch may be destructured using any suitable means. At leastpartial destructuring may be achieved through means including, but notlimited to: heating; enzyme modification; chemical modificationincluding but not limited to ethoxylation and the like (such as byadding ethylene oxide for example); chemical degradation; andcombinations thereof. Agents that may act as starch plasticizers may beused to destructure the starch. In some embodiments, these agents mayremain mixed with the starch during further processing. In otherembodiments, the agents may be transient, meaning that they are removedso that they are not present during further processing, and/or in thefinal plastic article.

In some embodiments, destructured starch may encompass native starchthat has been destructured by modification, as discussed above. Modifiedstarch is defined as a native starch that has had its native molecularcharacteristics (molecular weight or chemical structure) altered in anyway. For example, in some embodiments, if the molecular weight of thenative starch is changed, but no other changes are made to the nativestarch, then the starch can be referred to as a modified starch.Chemical modifications of starch typically include acid or alkalihydrolysis and oxidative chain scission to reduce molecular weight andmolecular weight distribution. Native starch generally has a very highaverage molecular weight and a broad molecular weight distribution (e.g.native corn starch has an average molecular weight of up to about60,000,000 grams/mole (g/mol)). The average molecular weight of starchcan be reduced as desired for the present invention by acid reduction,oxidation reduction, enzymatic reduction, hydrolysis (acid or alkalinecatalyzed), physical/mechanical degradation (e.g., via thethermomechanical energy input of the processing equipment), andcombinations thereof. The thermomechanical method and the oxidationmethod offer an additional advantage when carried out in situ. The exactchemical nature of the starch and molecular weight reduction method isnot critical as long as the average molecular weight is in an acceptablerange. Ranges of weight average molecular weight for starch or starchblends added to the melt can be from about 3,000 g/mol to about8,000,000 g/mol, from about 10,000 g/mol to about 5,000,000 g/mol, orfrom about 20,000 g/mol to about 3,000,000 g/mol. In other embodiments,the weight average molecular weight is otherwise within the above rangesbut about 1,000,000 or less, or about 700,000 or less. Starches havingdifferent molecular weights may be mixed as desired for use in theinvention.

In some embodiments, destructured starch encompasses substituted starch.Substituted starches are starches that have some of their alcohol (i.e.,hydroxyl) functional groups replaced by other chemical moieties. Ifsubstituted starch is desired, chemical modifications of starchtypically include etherification and esterification. Chemicalmodification can be accomplished using ethylene oxide, otherwise knownas ethoxylation, resulting in destructured starch as discussed above.Substituted starches may be desired for better compatibility ormiscibility with the thermoplastic polymer and polyhydric alcohol.However, it may be desirable to balance substitution with the reductionin the rate of degradability. The degree of substitution of thechemically substituted starch is typically from about 1% to about 100%(i.e., completely substituted). Alternatively, a low degree ofsubstitution, from about 1% to about 6%, may be used.

In some embodiments, the starch compositions or the thermoplasticcompositions of the present invention comprise from about 1% to about99%, from about 30% to about 90%, from about 50% to about 85%, or fromabout 55% to 80% of starch, including the bound water content of thestarch. The starch is selected from the group consisting of nativestarch, destructured starch (which may include modified starch and/orsubstituted starch) and combinations thereof. The term “bound water”refers to the water found naturally occurring in starch before it ismixed with other components to make the composition. In contrast, theterm “free water” refers to water that may be added to a composition ofthe present invention. For example, free water may be incorporated as orwith a plasticizer. A person of ordinary skill in the art will recognizethat once the components are mixed in a composition, water can no longerbe distinguished by its origin. Starch that has not been subjected todrying processes typically has bound water content under ambientconditions of about 5% to about 16% by weight of starch. In someembodiments of the present invention, the compositions and products ofthe invention comprise at least about 50% destructured starch, or atleast about 60% destructured starch.

Starch of use in the present invention may comprise any combination ofstarches as described generally or specifically herein, or as known inthe art. Suitable starches of use may be selected from the groupconsisting of: cold water insoluble starch; cold water soluble starch;and combinations thereof. Wherein “cold water” refers to water that isat or below 25° C. As used herein, cold water insoluble starch is starchthat dissolves less than 25% in water at 25° C.

Thermoplastic starch used herein refers to a starch composition that iscapable of flowing when at an elevated temperature (significantly abovenormal ambient temperature; generally above 80° C.), to the extent thatthe starch, or a composition comprising the starch, can be shaped intoplastic articles. The plastic articles are capable of solidifying afterthe elevated temperature is lowered to ambient temperatures to retainthe shaped form.

Polyhydric Alcohol

“Polyhydric alcohol” as used herein refers to an alcohol having two ormore alcohol (i.e., hydroxyl) functional groups. Without wishing to bebound by theory, it is believed (as mentioned above) that polyhydricalcohol may act as a starch plasticizer in the starch compositions ofthe present invention. In other words, polyhydric alcohol is believed toenable the starch to flow and to be processed, i.e., to create athermoplastic starch.

Any suitable polyhydric alcohol or combination of polyhydric alcohols isof use. Non-limiting examples of suitable polyhydric alcohols include:glycerol (also known in the art as glycerin), glycol, sugar, sugaralcohol, and combinations thereof. Non-limiting examples of glycols ofuse include: ethylene glycol, propylene glycol, dipropylene glycol,butylene glycol, hexane triol, and the like, polymers thereof, andcombinations thereof. Non-limiting examples of sugars of use include:glucose, sucrose, fructose, raffinose, maltodextrose, galactose, xylose,maltose, lactose, mannose, erythrose, pentaerythritol, and mixturesthereof. Non-limiting examples of sugar alcohols of use include:erythritol, xylitol, malitol, mannitol, sorbitol, and mixtures thereof.In specific embodiments of the present invention, the polyhydric alcoholcomprises glycerol, mannitol, sorbitol, and combinations thereof.

In general, the polyhydric alcohol is substantially compatible with thepolymeric components with which it is intermixed. As used herein, theterm “substantially compatible” means that when heated to a temperatureabove the softening and/or the melting temperature of the composition,the polyhydric alcohol is capable of forming a visually homogeneousmixture with polymer present in the component in which it is intermixed.In some embodiments, the plasticizer is water soluble.

In some embodiments of the present invention, the polyhydric alcohol mayalso be used as a destructuring agent for starch. In these embodiments,upon destructuring the starch, the polyhydric alcohol may act as aplasticizer to the destructured starch, thereby rendering itthermoplastic. In further embodiments, upon destructuring the starch,the polyhydric alcohol may be removed and substituted with a differentplasticizer to render the destructured starch thermoplastic. In someembodiments, the polyhydric alcohol may improve the flexibility of theresulting plastic articles.

Polyhydric alcohol is included in the present thermoplastic compositionsin any suitable amount for either destructuring starch and/or renderingdestructured starch thermoplastic. Generally, the amount of polyhydricalcohol needed is dependent upon the molecular weight of the starch, theamount of starch in the mixture, the affinity of the polyhydric alcoholfor the starch, and combinations thereof. The polyhydric alcohol shouldsufficiently render the starch component thermoplastic so that it can beprocessed effectively, for example to form plastic articles. Generally,the amount of polyhydric alcohol increases with increasing molecularweight of starch. Typically, the polyhydric alcohol can be present incompositions of the present invention in an amount of from about 2% toabout 70%, from about 5% to about 50%, from about 10% to 30%, or fromabout 15% to about 25%.

Acid

Acids of use in the present invention have at least one functional groupselected from the group consisting of: carboxylic acid, carboxylic acidanhydride, and combinations thereof. Such acids include, but are notlimited to, monoacids, diacids, polyacids (acids having at least threeacid groups), polymers comprising at least one acid moiety, co-polymerscomprising at least one acid moiety, anhydrides thereof, and mixturesthereof.

Non-limiting examples of acids of use include: adipic acid, sebaticacid, lauric acid, stearic acid, myristic acid, palmitic acid, oleicacid, linoleic acid, sebacic acid, citric acid, oxalic acid, malonicacid, succinic acid, glutaric acid, maleic acid, fumaric acid, phthalicacid, isophthalic acid, terphthalic acid, acrylic acid, methacrylicacid, itaconic acid, glycidyl methacrylate, and combinations thereof.Anhydrides of such acids may also be employed within the context of thepresent invention. Non-limiting examples of acid anhydrides of useinclude: maleic anhydride, phthalic anhydride, succinic anhydride andcombinations thereof.

Polymers and co-polymers comprising at least one acid moiety, and/ortheir anhydrides are of use. Suitable polymers and copolymers include,but are not limited to, those comprising monomer units of acrylic acid,methacrylic acid, itaconic acid, glycidyl methacrylate, anhydridesthereof, and combinations thereof. The polymer can contain other monomerunits in conjunction with these acid monomer units. For example,ethylene-acid monomer copolymers such as ethylene-acrylic acid copolymercan be used. In a specific embodiment, the copolymers comprise at least50 mol % of acid monomer units. The molecular weight of such polymersand copolymers can vary from as low as about 2,000 to over about1,000,000. An example of a suitable polyacrylic acid is from AldrichChemical Company, having a molecular weight of about 450,000. An exampleof a suitable ethylene-acrylic acid copolymer is Primacore 59801 fromDow Chemical, having an acrylic acid content of at least 50 mol %.

In specific embodiments, the acid comprises at least one diacid,polyacid, acid polymer or copolymer, or a mixture thereof. In otherembodiments, the acid comprises a diacid, alone or in combination withanother acid, for example a monoacid. In further embodiments, the acidcomprises adipic acid, stearic acid, lauric acid, citric acid,polyacrylic acid and/or ethylene-acrylic acid copolymer.

Typically, the acid is employed in the starch composition in an amountof from about 0.1% to about 30%, from about 1% to about 20%, or fromabout 2% to about 12%. In some embodiments, the molar ratio of alcoholfunctional groups to acidic functional groups in the starch compositionis at least about 1:1, or at least about 4:1. In some embodiments, themolar ratio of alcohol functional groups to acidic groups in the starchcomposition is from about 1:1 to about 200:1, or from about 1:1 to about50:1.

Triglyceride

Any suitable triglycerides, which are also known in the art astriacylglycerols, are of use in the present invention. Non-limitingexamples of triglycerides of use include: tristearin, triolein,tripalmitin, 1,2-dipalmitoolein, 1,3-dipalmitoolein,1-palmito-3-stearo-2-olein, 1-palmito-2-stearo-3-olein,2-palmito-1-stearo-3-olein, trilinolein, 1,2-dipalmitolinolein,1-palmito-dilinolein, 1-stearo-dilinolein, 1,2-diacetopalmitin,1,2-distearo-olein, 1,3-distearo-olein, trimyristin, trilaurin andcombinations thereof.

Suitable triglycerides may be added to the present compositions in neatform. Additionally, or alternatively, oils and/or processed oilscontaining suitable triglycerides may be added to the compositions.Non-limiting examples of oils include coconut oil, corn germ oil, oliveoil, palm seed oil, cottonseed oil, palm oil, rapeseed oil, sunfloweroil, whale oil, soybean oil, peanut oil, linseed oil, tall oil, andcombinations thereof.

Typically, triglycerides are employed in the starch compositions in anamount of from about 0.1% to about 30%, from about 1% to about 20%, orfrom about 2% to about 12%. In some embodiments, the molar ratio ofalcohol functional groups to ester functional groups in the starchcomposition is at least about 1:1, or at least about 4:1. In someembodiments, the molar ratio of alcohol functional groups to esterfunctional groups in the starch composition is from about 1:1 to about200:1, or from about 1:1 to about 50:1.

In some embodiments, combinations of acid and triglyceride are employedin the starch compositions. In some embodiments, the total amounts ofacid and triglyceride is from about 0.1% to about 32%, from about 1% toabout 25%, or from about 2% to about 20%. Additionally, oralternatively, the molar ratio of the alcohol functional groups to thetotal of ester and acid functional groups is at least about 1:1, or atleast about 4:1. In some embodiments, the molar is from about 1:1 toabout 200:1, or from about 1:1 to about 50:1.

Additional Components

The compositions according to the present invention may include one ormore additional components as desired for the processing and/or end useof the composition. Additional components may be present in any suitableamount. In some embodiments, additional components may be present in anamount of from about 0.01% to about 35% or from about 2% to about 20%.Non-limiting examples of additional components include, but are notlimited to, additional polymers, fillers, processing aids and the like.

Non-limiting examples of additional polymers of use include:polyhydroxyalkanoates, polyvinyl alcohol, polyethylene, polypropylene,polyethylene terephthalate, maleated polyethylene, maleatedpolypropylene, polylactic acid, modified polypropylene, nylon,caprolactone, and combinations thereof.

In embodiments in which properties including, but not limited to,biodegradability and/or flushability are desired, additional suitablebiodegradable polymers and combinations of thereof are of use. In someembodiments, polyesters containing aliphatic components are suitablebiodegradable thermoplastic polymers. In some embodiments, among thepolyesters, ester polycondensates containing aliphatic constituents andpoly(hydroxycarboxylic) acid are preferred. The ester polycondensatesinclude, but are not limited to: diacids/diol aliphatic polyesters suchas polybutylene succinate, and polybutylene succinate co-adipate;aliphatic/aromatic polyesters such as terpolymers made of butylenesdiol, adipic acid, and terephthalic acid. The poly(hydroxycarboxylic)acids include, but are not limited to: lactic acid based homopolymersand copolymers; polyhydroxybutyrate; and other polyhydroxyalkanoatehomopolymers and copolymers. In some embodiments, a homopolymer orcopolymer of poly lactic acid is preferred. Modified polylactic acid anddifferent stereo configurations thereof may also be used. Suitablepolylactic acids typically have a molecular weight range of from about4,000 g/mol to about 400,000 g/mol. Examples of suitable commerciallyavailable poly lactic acids include NATUREWORKS™ from Cargill Dow andLACEA™ from Mitsui Chemical. An example of a suitable commerciallyavailable diacid/diol aliphatic polyester is the polybutylenesuccinate/adipate copolymers sold as BIONOLLE™ 1000 and BIONOLLE™ 3000from the Showa Highpolmer Company, Ltd. Located in Tokyo, Japan. Anexample of a suitable commercially available aliphatic/aromaticcopolyester is the poly(tetramethylene adipate-co-terephthalate) sold asEASTAR BIO™ Copolyester from Eastman Chemical or ECOFLEX™ from BASF. Insome embodiments, the biodegradable polymer or combination of polymersmay comprise polyvinyl alcohol.

The aforementioned biodegradable polymers and combinations thereof maybe present in an amount of from about 0.1% to about 70%, from about 1%to about 50%, or from about 2% to about 25%, by weight of the presentstarch and thermoplastic starch compositions. Non-limiting examples offillers include: talc, clay, pulp; flour, walnut shells, cellulose,cotton, jute, raffia, rice chaff, animal bristles, chitin, granularstarch, diatomaceous earth, nanoparticles, carbon fibers, kenaf, andcombinations thereof.

Processing aids are generally present in the current compositions inamounts of from about 0.1% to about 3%, or from about 0.2% to about 2%.Non-limiting examples of processing aids include: lubricants, anti-tack,polymers, surfactants, oils, slip agents, and combinations thereof.Non-limiting examples of specific processing aids include: Magnesiumstearate; fatty acid amides; metal salts of fatty acids; wax acid estersand their soaps; montan wax acids, esters and their soaps; polyolefinwaxes; non polar polyolefin waxes; natural and synthetic paraffin waxes;fluoro polymers; talc; silicon; clay; diatomaceous earth. Commercialexamples of such compounds include, but are not limited to: Crodamide™(Croda, North Humberside, UK), Atmer™ (Uniqema, Everberg, Belgium,) andEpostan™ (Nippon Shokobai, Tokyo, JP). In some embodiments, the starchcomprises at least about 50% of all polymer components in the starchcompositions, more specifically at least about 60% of all polymercomponents in the starch compositions.

Water Stability

Without wishing to be bound by theory, the thermoplastic polymercompositions according to the present invention may be rendered waterstable via the aforementioned ester condensation reaction and/ortransesterification reaction. When the thermoplastic polymercompositions are made into plastic articles, the reactions may beinduced before formation of the article, during formation of thearticle, after the article's formation (i.e., curing) and combinationsthereof. In some embodiments, the reaction(s) are induced, and/or driventowards completion through the application of heat. In some embodimentsof the present invention, a catalyst may be used to initiate and/oraccelerate the ester condensation and/or transesterification reactions.Any suitable catalyst is of use. Non-limiting examples of usefulcatalysts include Lewis acids. A non-limiting example of a Lewis acid ispara-toluene sulfonic acid.

With regard to the ester condensation reaction, it is believed withoutbeing bound by theory that the heating of the thermoplastic polymercomposition comprising acid, may remove a sufficient amount of waterfrom the starch composition, (including some, but not all of the boundwater) to induce a reaction of the polyhydric alcohol and the acid toform a water stable reaction product to an extent that provides theresulting composition with water stability. While again not wishing tobe bound by theory, it is believed that a condensation reaction mayoccur between the polyhydric alcohol and acid. Generally, the chemistrywhich governs such condensation reactions is known in the art as alkydchemistry.

In the present invention, it may be important that the estercondensation reaction is not completed to such an extent that a gel ofthe reaction products is formed before final processing of thethermoplastic composition occurs. As used herein “gel” means a materialthat is crosslinked to an extent that flow even under high temperaturesis no longer possible without degradation of the material's molecularweight. It is important for the system to be below the gel point of thereactants before final processing so as to retain sufficient flowbehavior to enable shaping of the material into plastic articles,including but not limited to fibers. The gel point is defined as thestate at which enough polymer chains formed by the products of thereactants are bonded together such that at least one very large moleculeis coextensive with the polymer phase and flow is no longer possible andthe material behaves more like a solid.

Up until to the gel point, it may be advantageous for the reaction toproceed to a point where prepolymers such as oligomers or even largermolecules are formed, yet these species should retain the ability toflow and be shaped into useful articles. Oligomers as used herein arereaction products from constituent monomers that include at least twomonomers and up to about ten monomers. In some embodiments of thecurrent invention, when carrying out the ester condensation reactionbetween the acid and alcohol and thereby forming oligomers, it may beadvantageous to remove excess water from the reaction product beforeforming the end product. It is believed that removal of the water mayspeed the ester condensation reaction toward completion in the finalprocessing step.

In some embodiments, the thermoplastic composition is heated at atemperature of at least about 90° C., more specifically at least about100° C., to convert the thermoplastic composition to a water stablecomposition. Typically, the thermoplastic composition will not be heatedat a temperature over about 250° C., or over about 225° C. In someembodiments, the thermoplastic composition is heated at a temperature ofat least about 115° C. to convert the thermoplastic composition to awater stable composition. In further embodiments, the thermoplasticcomposition is heated at a temperature of from about 130° C. to about180° C. to convert the thermoplastic composition to a water stablecomposition. In some embodiments, the water content of the compositionis reduced to a level below the level of bound water naturally presentin the starch at ambient conditions. In other embodiments, the watercontent of the composition is reduced to 5% or less of the composition.In other embodiments, water content is about 4% or less. In anotherembodiment the water content is reduced to about 3% or less. In yetanother embodiment, the water content is reduced to about 2% or less.Water content can be reduced by providing the starch composition atelevated temperatures under conditions wherein water can vaporize.

Although not required, the physical form of the thermoplastic polymercomposition may be modified to provide a greater surface area tofacilitate water removal from the compositions. The heating timenecessary to convert a thermoplastic composition to a water stable formwill depend, in general, on a variety of factors, including componentcompositions (i.e., particular starch, polyhydric alcohol and acidand/or triglyceride), heating temperature, physical form of thecomposition, and the like. Suitable times may range from instantaneouslyto about 24 hours, about 1 minute to about 24 hours, from about 5minutes to about 12 hours, or from about 5 minutes to about 1 hour. Ingeneral, water content should not be reduced under conditions whereindecomposition, burning or scorching of the starch occurs, particularlyin the case that visually noticeable or significant levels ofdecomposition, burning or scorching occurs.

In some embodiments, the thermoplastic compositions according to thepresent invention are formed by melt mixing and/or extruding a mixturecomprising destructured starch, polyhydric alcohol, and acid and/ortriglyceride, using conventional mixing and/or extrusion techniques. Themixture may be formed by combining destructured starch, polyhydricalcohol, and acid and/or triglyceride. Alternatively, the mixture may beprovided by combining non-destructured starch, polyhydric alcohol, andacid and/or triglyceride, with the additional step of destructuring thestarch in situ in the mixture, by any of the destructuring techniquesdiscussed above. The components are typically mixed using conventionalcompounding techniques. The objective of the compounding step is toproduce at least a visually homogeneous melt composition comprising thestarch.

A suitable mixing device is a multiple mixing zone twin screw extruderwith multiple injection points. The multiple injection points can beused to add the destructured starch, polyhydric alcohol and acid and/ortriglyceride. A twin screw batch mixer or a single screw extrusionsystem can also be used. As long as sufficient mixing and heatingoccurs, the particular equipment used is not critical. An alternativemethod for compounding the materials comprises adding the starch,polyhydric alcohol, and acid and/or triglyceride to an extrusion systemwhere they are mixed in progressively increasing temperatures. Forexample, a twin screw extruder with six heating zones may be employed.This procedure can result in minimal thermal degradation of the starchand may ensure that the starch is fully destructured. However, it maynot be necessary to extrude a melt mixture, and, in general, any methodknown in the art or suitable for the purposes hereof can be used tocombine the ingredients of the components to form the thermoplasticcompositions of the present invention. Typically such techniques willinclude heat and mixing, and optionally pressure. The particular orderor mixing, temperatures, mixing speeds or time, and equipment can bevaried, as will be understood by those skilled in the art, howevertemperature should be controlled such that the starch does notsignificantly degrade. Further, if the temperature of the melt mixingand/or extrusion process is sufficiently high and for a sufficient timeto eliminate at least a portion of bound water from the starch and drivea reaction between the polyhydric alcohol and the acid, thethermoplastic composition which is formed by melt extruding thesecomponents will convert to a water stable composition. For example, themelt extrusion can be conducted in an extruder provided with vents orother modifications which facilitate water removal and the conversion toa water stable composition. In such an embodiment, it is thereforeadvantageous to melt extrude the composition to a form which is suitablefor end use, for example, as films, sheets, adhesives, binders,laminates, coatings, and foams; molded articles; and combinationsthereof.

On the other hand, if the temperature or conditions at which the meltextrusion of the mixture comprising destructured starch, polyhydricalcohol and acid and/or triglyceride is conducted at a sufficiently lowtemperature and/or for an insufficient time to eliminate at least aportion of bound water from the starch and drive reaction between thepolyhydric alcohol and the acid and/or triglyceride, the resultingextrudate comprises thermoplastic compositions of the invention, whichmay be further processed, if desired, and which are convertible to waterstable compositions by further heating. The extrudate can therefore beprovided in this embodiment in a form which facilitates handling,further processing, or the like. For example, a thermoplasticcomposition extrudate can be in pellet form, powder or crumb form or thelike. In a specific embodiment, the thermoplastic composition extrudateis in a pellet form which is then suitable for melt extruding to adesired end use form. In this embodiment, the further melt extrusion ofpellets (or extrudate of another form) to form films, sheets, adhesives,binders, laminates, coatings, and foams; molded articles, or otherdesired product forms, may be conducted under sufficient conditions oftemperature and time to effect the conversion of the thermoplasticcomposition to a water stable composition or product. Alternatively, ifthe melt extrusion is not conducted under sufficient conditions oftemperature and time to effect the conversion of the thermoplasticcomposition to a water stable composition, the resulting extrudate maybe heated further to effect the conversion of the extruded thermoplasticcomposition to a water stable product.

In some embodiments, a thermoplastic composition in the form of pelletsis formed by melt extruding destructured starch, polyhydric alcohol andacid and/or triglyceride. The extrusion process may not providesufficient heating of the thermoplastic composition for a sufficienttime to effect conversion to a water stable composition. The pellets aresubsequently subjected to melt extrusion by conventional fiber spinningprocesses. The resulting fibers are rendered water stable by anadditional heating step at a temperature of from about 100° C., morespecifically 115° C., still more specifically from about 130° C., toabout 180° C. Alternatively, the melt spinning process is conducted at atemperature in this range under conditions by which the resulting fibersare rendered water stable. In a further embodiment, the necessary wateris eliminated from the fibers by flash evaporation as the fibers exitthe spinneret swing to the reduction in pressure.

In some embodiments, it may be advantageous to provide the polyhydricalcohol and the acid and/or triglyceride as what is termed herein as a“pre-polymer”. In these instances, the aforementioned condensationreaction and/or transesterification reaction has already at leastpartially, but not completely, taken place between the polyhydricalcohol and the acid and/or triglyceride before it is mixed with thestarch. In further embodiments, the pre-polymer may also contain starch.Pre-polymers may take any suitable form which may be convenient to make,ship process and combinations thereof. Non-limiting examples of formsinclude strands, pellets, powder, and combinations thereof.

Methods

The water stability of compositions and articles comprisingthermoplastic starch is measured in the following way. 1000 ml of tapwater is charged to a clean glass beaker. A sample of the thermoplasticstarch composition, or article comprising the thermoplastic starchcomposition, is placed in the water. The particular size of the testpiece can vary depending on the type of article and method ofconstruction, but in general the smallest dimension of the test pieceshould be smaller than 5 mm. Specific sizes for various forms are:

Sheet or Laminate: 5 cm×5 cm 0.5 mm—(no more than 0.5 mm thick)

Film, or Coating: 5 cm×5 cm×0.25 mm—(no more than 0.3 mm thick)

Molded Article: 2.5 cm×0.6 cm×0.7 mm—(no more than 1 mm thick)

Adhesive or binder: 5.0 cm×5.0 cm×0.5 mm—(no more than 1 mm thick)

Foam: 2.0 cm×2.0 cm×0.5 cm

A stir bar is added and the contents are stirred at least 30 rpm for 24hours. After 24 hours the test piece is removed and dried at roomtemperature for 24 hours. The piece is measured again, and if thedimensions of the sheet change along any length by less than 10% thenthe piece and consequently the thermoplastic composition or article fromwhich the test piece is made, is said to display water stability.

Plastic Articles

As used herein, “plastic article” is meant to encompass articles madesolely from, or having at least one portion made from, thermoplasticcompositions according to the present invention. Plastic articlesinclude, but are not limited to extruded articles such as: films,sheets, adhesives, binders, laminates, coatings, and foams; moldedarticles; and combinations thereof.

Personal hygiene articles and absorbent articles may be plastic articlesor comprise plastic articles made from thermoplastic polymercompositions of the present invention.

Extruded Articles Films

In some embodiments of the present invention, the plastic article is afilm. As used herein, “film” means an extremely thin continuous piece ofa substance having a high length to thickness ratio and a high width tothickness ratio, “high” meaning a ratio of over about 10:1. While thereis no requirement for a precise upper limit of thickness, an upper limitwould be about 0.254 mm, about 0.01 mm, or about 0.005 mm

The films of the present invention can be employed in a variety ofdisposable products including, but not limited to, disposable personalhygiene articles (e.g., diapers, catamenials and the like),shrink-wrapping (e.g., food wraps, consumer product wraps, pallet and/orcrate wraps, and the like), or bags (grocery bags, food storage bags,sandwich bags, resealable “Ziploc®”-type bags, garbage bags, and thelike). The protective value of the present films, much like other films,may depend on its being continuous, i.e., without holes or cracks, suchthat it may serve as an efficient barrier to molecules such asatmospheric water vapor, and/or oxygen. In some embodiments of thepresent invention, the films are liquid impervious and suitable for usein absorbent disposable sanitary items including, but not limited to,disposable diapers, feminine hygiene pads and the like.

Films of the present invention may have a number of physicalcharacteristics, such as biodegradability and compostability, forexample. Films that perform well as compostable backsheets in personalhygiene articles including, but not limited to, diapers and femininehygiene pads, may have characteristics such as those described in U.S.Pat. No. 5,498,692.

The films of the present invention may be made using any suitableprocess that is used for producing single or multilayer films.Non-limiting examples of methods of use include cast film blowing, castfilm extrusion and blown film extrusion. These methods as well as othersuitable methods are described in U.S. Pat. No. 5,498,692.

In some embodiments, strands, pellets, or powders made from thepresently disclosed thermoplastic polymer compositions, as well ascombinations thereof, are dry blended and melt mixed in a film extruder.In embodiments in which insufficient mixing occurs in the film extruder,the strands, pellets, powders and combinations thereof, can be first dryblended and then melt mixed in a pre-compounding extruder followed byre-pelletization prior to film extrusion.

Sheets

In another embodiment of the present invention, the plastic article is asheet. As used herein, “sheet” means a very thin continuous piece of asubstance, having a high length to thickness ratio (over about 10:1) anda high width to thickness ratio (over about 10:1), wherein the materialis thicker than about 0.254 mm Sheeting may share many of the samecharacteristics as film in terms of properties and manufacture. However,sheeting may be stiffer than film, and may have a self-supportingnature. Differences in stiffness and support may arise as result ofmodification of the film manufacturing methods. Any suitablemanufacturing method is of use. A non-limiting example of one method iscast extrusion. This method, as well as others, is described in U.S.Pat. No. 5,498,692.

Adhesives

In another embodiment of the present invention, the plastic article isan adhesive. As used herein “adhesive” means a material that joins twoother materials, called adherends, together. A general discussion onadhesives can be found in the Encyclopedia of Polymer Science andEngineering, Vol. 1, pp. 547-577, (hereafter referred to as “EPSE-6”).In some embodiments of the present invention, the adhesive is applied asa liquid, optionally of a low viscosity. In the liquid form, theadhesive wets and flows into the crevices of the adherend. The liquidform of the adhesive is obtained by heating to the point that flowoccurs, dissolving or dispersing the material in a solvent, or startingwith liquid monomers or oligomers that polymerize or react afterapplication. The adhesive then undergoes a phase change to a solideither by cooling, solvent evaporation, or reaction, in order for thejoint to acquire the necessary strength to resist shearing forces.However, pressure-sensitive adhesives are an exception, since no phasechange occurs.

The thermoplastic polymer compositions, or the starch compositions, ofthe present invention may be processed into a variety of adhesives,including but not limited to, hot melt, solution, dispersion andpressure sensitive adhesives.

As used herein, “hot-melt adhesive” refers to a thermoplastic polymercomposition according to the present invention, which is heated toobtain a liquid of flowable viscosity, and after application to anadherend, cooled to obtain a solid. Generally, the molecular weight ofthe adhesive is tailored to provide flowability in the melt, but stillbe strong enough in the solid form to resist shearing forces experiencedin the application. The primary feature of hot-melt adhesives is theability of the thermoplastic material to flow above a certaintemperature, high above the normal use temperature of the bond. Uponcooling, the material hardens, either by passing through the glasstransition temperature of one of the components, or the crystallizationtemperature. This hardening lends physical integrity to the bond.

The adhesives of the present invention may be applied in any suitableway. Non-limiting examples of application include applying the adhesivesas solutions, in water or an organic solvent, or in the form of aqueousdispersions. In either form, the solvent is removed after applicationfor the adhesive to attain the required solid form. The solution ordispersion is usually applied to one of the surfaces to be bonded, andthe solvent removed before the second surface is joined; often, heatingis required to expedite the drying step. With porous substrates, such aspaper or wood, final drying can take place after formation of the joint.Solids contents of the solutions vary from 5 to 95%, although valuesfrom 20 to 50% are most common.

As used herein, “dispersion” refers to adhesives prepared by trueemulsion polymerization or dispersed as larger particles in some carrierfluid. In addition to their economic advantage, dispersions containing40-50% solids offer lower viscosity than solutions, even if the solidsare high molecular-weight polymers (EPSE-6). Adhesive dispersions of thepresent invention may be prepared by high shear in the presence ofsurfactants to obtain waterborne formulations, procedures which are wellknown to those skilled in the art.

Unlike the other adhesives disclosed herein, pressure sensitiveadhesives comprising the thermoplastic polymers of the presentinvention, do not change their physical state from the initialapplication, to the final breaking of the adhesive bond. They remainpermanently deformable, and may alter under even slight application ofpressure. Pressure sensitive adhesives that are in dry form arepermanently tacky at room temperature and firmly adhere to surfaces uponmere contact. The most common form of pressure-sensitive adhesive is ona backing, usually in tape form. Common masking tape, for example, ismanually applied after the user removes the desired length from a roll.Many bandages are held to the skin by pressure-sensitive adhesives.

Binders

TPS materials can be used as adhesives or “binders” in any suitableapplications, including but not limited to nonwoven materials,composites and the like. As used herein, a “binder” is an adhesivesubstance used in joining the fiber elements of a web in order toprovide the fiber web cohesion integrity and or strength. In someembodiments comprising longer fiber nonwovens, the nonbonded materialmay be formed and then coated using the art recognized “dip” coatingprocess, wherein the nonwoven is run through a bath of adhesive in adispersion or solution, such as a colloidal dispersion in water. Theadhesive then dries or sets and is optionally pressed to provide thebonded nonwoven. For materials lacking the mechanical integrity towithstand dip coating, spray coating may be used. Spray coating uses asprayed adhesive including, but not limited to, a heated waterdispersion of the adhesive, which then dries or cures and is optionallypressed to provide the bonded nonwoven.

For other materials which are made from fibers, the binding materialscan be fibers themselves mixed within the web. These fibers canpartially or completely melted and refused upon heating and cooling toprovide cohesion of the web. The binder fibers can be made wholly of thebinding material or just a part as in core shell arrangement in a fiberwhere the shell is the binder material.

Laminates

In some embodiments of the present invention, the aforementioned filmsand/or sheets are of use to laminate a substrate including, but notlimited to, paper. The film and/or sheet may be all or part of amultilayer substrate, i.e., a laminate or composite. A laminate isdefined as two or more substrates joined together. A laminate may haveone or more layers comprising a blended starch composition as set forthherein. In another embodiment, a laminate may have a first layercomprising a thermoplastic starch composition as described herein and asecond layer comprising a paper layer. In some embodiments, the laminatemay also have a first layer comprising a polypropylene polymer, a secondlayer comprising a thermoplastic starch, and a third layer comprisingpolypropylene, or any combination of desired layers. As used herein, theterms first, second, or third layers are meant to describe separatelayers and are not intended to be limiting as to the location of thelayer. In one embodiment of the invention, a laminate has three layerswherein the outer two layers comprise a thermoplastic starch compositionand the intermediate layer comprises a paper or paperboard material suchas cardboard.

Coatings

As used herein, the term “coating” refers to both a layer exclusively onthe surface of a substrate as well as a layer which to some degreepenetrates the substrate. Suitable substrates include, but are notlimited to, synthetic or bio sourced polymer film, paper, fabric, threadand yarn. Often the substrate will be paper. As used herein, “paper”refers to a substrate formed from cellulose fiber, including paper andcardboard. As used herein, “fabric” includes natural and syntheticfabrics. The fabrics may be knitted, woven or non-woven. Suitablefabrics include cotton, rayon, wool, and polyesters, as well asbiodegradable fabrics. As used herein, “thread and yarn” include naturaland synthetic threads and yarns, such as cotton, rayon, polyester, wool,silk, nylon, and acrylic as well as biodegradable threads. As usedherein, “fiber” refers to a flexible, macroscopically homogeneous bodyhaving a high length-to-width ratio (over about 10:1) and a small crosssection.

The coating may be applied to one or two sides of a substrate such aspaper or fabric. Fabric and paper coated with the thermoplastic starchcompositions of the present invention can be used to form items withimproved water stability, such as wrapping paper, paper bags, plasticbags, cardboard containers, drink boxes, trays, table clothes, napkins.

The coatings may serve any suitable purpose including, but not limitedto, use as barriers, decorative coatings, or for other purposes such asimproving printing. Coatings may be used to apply adhesive forlaminating one web to another or for manufacturing of pressure-sensitivetapes and labels. Coatings may also be used for saturation of a porousweb substrate, such as paper, in order to improve its stability tomoisture or to improve its strength.

The thickness of a coating is generally measured in “mils” One mil isequal to about 0.001 inch. The substrates generally have a coating up toabout 5, from about 4 to about 0.5, or from about 2 to about 1, milsthick. Paper substrates generally have a coating with a thickness offrom about 5 to about 0.5, or from about 2 to e.g., about 1, mils, whilefabric substrates generally have a coating with a thickness of fromabout 5 to about 1, or from about 3 to about 2, mils Thread and yarnsubstrates generally have a thinner coating than paper or fabricsubstrates, such as a thickness of from about 2 to about 0.2, or fromabout 1 to about 0.5, mils

The coatings may comprise additives such as colorants. In someembodiments, such colorants are nonfugitive. As used herein,“nonfugitive” refers to an additive that does not escape from the TPS ata faster rate than which the material biodegrades. The coatings hereinmay be formed from a composition comprising the TPS and colorant.Alternatively, colors and designs may be printed on the items aftermanufacture. Preferably the colorants are non-toxic. Some items, such asgarbage bags, may have coatings comprising deodorants, fragrances ordisinfectants.

Coated articles may be formed using any conventional coating techniquesor coating equipment. Coating techniques include, but are not limitedto, extrusion coating, roller coating, brush coating, dip coating, spraycoating, electrostatic coating, centrifugal coating and cast coating.Articles may be coated with melted TPS, and then exposed to a coolant,such as water or air. Substrates may be laminated with a sheet or filmcomprising TPS, such as a solution cast film or a melt pressed film.Slurries, or suspensions comprising TPS may be applied to a substrate,and the substrate then allowed to dry and, optionally, pressed.

Coatings applied in a non-solid form must be sufficiently fluid to bespread into a uniformly thin layer across the substrate. Therefore,coatings are typically applied as emulsions, as a hot melt (solid moltenor softened by heat). Extrusion coating is similar to hot-melt coating.In extrusion coating, a film of molten polymer is deposited between twomoving webs in a nip created by a rubber pressure roll and achrome-plated steel chill roll.

Coatings may be applied to the web material wound in rolls, or to precutsheets. Items such as disposable plates and trays may be formed bypressing coated paperboard blanks between forming dies, as disclosed inU.S. Pat. No. 5,776,619.

Foams

In another embodiment of the present invention, the plastic article isfoam. As used herein, “foam” refers the thermoplastic compositions ofthe present invention the apparent density of which has beensubstantially decreased by the presence of numerous cells distributedthroughout its bulk (see ASTM D 883-62T, American Society for Testingand Materials, Philadelphia, Pa., (1962)). Such two-phase gas/solidsystems in which the solid is continuous and composed of a syntheticpolymer or rubber include cellular polymers (or copolymers), expandedplastics and foamed plastics (ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, Vol.11, John Wiley & Sons, New York (1980)).

The gas phase may be distributed into pockets or voids called “cells”which are classified into two types, open and closed. Open-celledmaterials are foams the cells of which are inter-connected such thatgases may pass freely through the cells. Closed-cell materials havecells that are discrete and isolated from each other.

Foams are further categorized into flexible and rigid foams. Thisclassification is based on a particular ASTM test procedure (see ASTM D,Vol. 37, pp. 1566-1578, American Society of Testing and Materials,Philadelphia, Pa., (1978)). Flexible foam is foam which does not rupturewhen a 20×2.5×2.5 cm piece is wrapped around a 2.5 cm mandrel at auniform rate of 1 lap/5 s at 15-25° C. Foams that do rupture under thistest are referred to as rigid foams.

Foams according to the present invention may find any suitable usedincluding, but not limited to, packaging, comfort cushioning,insulation, structural components and the like. In some areas ofpackaging, a foamed material having increased biodegradability and/orcompostability would offer superior benefits to packaging that iscurrently used, such as polystyrene, paper and starch foams for example.In hot food containers, polystyrene offers significantly higher thermalinsulation over the only currently degradable alternative, paper wraps.Foamed articles comprising the thermoplastic polymer compositions of thepresent invention have the thermal insulating properties of polystyrene,yet are biodegradable and/or compostable. These materials are ideal forhot food take-out and cold food packaging.

Foamed polystyrene chips are used as cushioned packing materials forconsumer and industrial goods. Many of these chips are disposed of inlandfills. Foamed chips comprising a thermoplastic polymer compositionof the present invention can perform like polystyrene yet have increasedbiodegradability and/or compostability. Moreover, foamed chips accordingto the present invention may be water stable.

The foams of the present invention may be made using any suitableprocess. Non-limiting examples of methods are described in U.S. Pat. No.5,498,692.

Molded Articles

In another embodiment of the present invention, the plastic article is amolded article. As used herein, “molded articles” refer to objects thatare formed from thermoplastic materials. The thermoplastic materials maybe, for example, injected, compressed, or blown by means of a gas intoshape defined by a female mold. These objects can be solid objects liketoys, or hollow like bottles and containers. Methods of making moldedarticles are described in further detail in U.S. Pat. No. 5,498,692.

Disposable Personal Care Products

The present invention further relates to disposable personal careproducts comprising thermoplastic polymer compositions of the presentinvention. In some embodiments, disposable personal care absorbentarticles comprise a liquid pervious topsheet, a liquid imperviousbacksheet comprising a film of the present invention, and an absorbentcore positioned between the topsheet and backsheet. In some embodiments,the personal care absorbent articles are compostable. Non-limitingexamples of such absorbent articles include infant diapers, adultincontinent briefs and pads, and feminine hygiene pads and liners.

Additional personal care products comprising a thermoplastic polymercomposition of the present invention include, but are not limited to:personal cleansing wipes; disposable health care products such asbandages, wound dressings, wound cleansing pads, surgical gowns,surgical covers, surgical pads; other institutional and health caredisposables such as gowns, wipes, pads, bedding items such as sheets andpillowcases, foam mattress pads.

Films of the present invention that are used as liquid imperviousbacksheets in absorbent articles of the present invention, such asdisposable diapers, typically have a thickness of from 0.01 mm to about0.2 mm, or from 0.012 mm to about 0.051 mm

In general, the liquid impervious backsheet is combined with a liquidpervious topsheet and an absorbent core positioned between the topsheetand the backsheet. Optionally, elastic members and tape tab fastenerscan be included. While the topsheet, the backsheet, the absorbent coreand elastic members may be assembled in a variety of well knownconfigurations, a preferred diaper configuration is described generallyin U.S. Pat. No. 3,860,003.

The topsheet may be soft-feeling, and non-irritating to the wearer'sskin. Further, the topsheet may be liquid pervious, permitting liquidsto readily penetrate through its thickness. A suitable topsheet may bemanufactured from a wide range of materials including, but not limitedto, porous foams, reticulated foams, apertured plastic films, naturalfibers (e.g., wood or cotton fibers), synthetic fibers (e.g., polyesteror polypropylene fibers) or from a combination of natural and syntheticfibers. In some embodiments, the topsheet is made of a hydrophobicmaterial to isolate the wearer's skin from liquids in the absorbentcore.

In one embodiment, the topsheet comprises staple-length fibers having adenier of about 1.5. As used herein, the term “staple-length fibers”refers to those fibers having a length of at least about 16 mm

There are a number of manufacturing techniques which may be used tomanufacture the topsheet. For example, the topsheet may be woven,non-woven, spunbonded, carded, and the like. In one embodiment, thetopsheet is carded, and thermally bonded by means well known to thoseskilled in the fabrics art. The topsheet may have a weight from about 18to about 25 g/m², a minimum dried tensile strength of at least about 400g/cm in the machine direction, and a wet tensile strength of at leastabout 55 g/cm in the cross-machine direction. In some embodiments of thepresent invention, the top sheet comprises a thermoplastic polymercomposition of the present invention.

The topsheet and the backsheet are joined together in any suitablemanner. As used herein, the term “joined” encompasses configurationswhereby the topsheet is directly joined to the backsheet by affixing thetopsheet directly to the backsheet, and configurations whereby thetopsheet is indirectly joined to the backsheet by affixing the topsheetto intermediate members which in turn are affixed to the backsheet. Inone embodiment, the topsheet and the backsheet are affixed directly toeach other in the diaper periphery by attachment means such as anadhesive or any other attachment means known in the art. For example, auniform, continuous layer of adhesive, a patterned layer of adhesive, oran array of separate lines or spots of adhesive may be used to affix thetopsheet to the backsheet. In some embodiments of the present invention,the adhesive comprises a thermoplastic polymer composition of thepresent invention.

Tape tab fasteners are typically applied to the back waistband region ofthe diaper to provide a fastening means for holding the diaper on thewearer. Any suitable tape tab fasteners are of use including, but notlimited to those disclosed in U.S. Pat. No. 3,848,594. Tape tabfasteners or other diaper fastening means are typically applied near thecorners of the diaper.

In some embodiments, diapers have elastic members disposed adjacent theperiphery of the diaper. The elastic members may be located along eachlongitudinal edge so that they tend to draw and hold the diaper againstthe legs of the wearer. The elastic members may be secured to the diaperin an contractible condition so that in a normally unrestrainedconfiguration the elastic members effectively contract or gather thediaper. The elastic members can be secured in a contractible conditionin at least two ways. For example, the elastic members may be stretchedand secured while the diaper is in an uncontracted condition.Alternatively, the diaper may be contracted, for example, by pleating,an elastic member secured and connected to the diaper while the elasticmembers are in their relaxed or unstretched condition.

The elastic members may take a multitude of configurations. For example,the width of the elastic members may be varied from about 0.25 mm toabout 25 mm or more; the elastic members may comprise a single strand ofelastic material or the elastic members may be rectangular orcurvilinear. Still further, the elastic members may be affixed to thediaper in any of several ways which are known in the art. For examplethe elastic members may be ultrasonically bonded, heat and pressuresealed into the diaper using a variety of bonding patterns, the elasticmembers may simply be glued to the diaper and the like. In someembodiments of the present invention, the elastic members comprise athermoplastic composition of the present invention.

The absorbent core of the diaper is positioned between the topsheet andbacksheet. The absorbent core may be manufactured in a wide variety ofsizes and shapes (e.g., rectangular, hour-glass, asymmetrical, etc.) andfrom a wide variety of materials. The total absorbent capacity of theabsorbent core should, however, be compatible with the designed liquidloading for the intended use of the absorbent article or diaper.Further, the size and absorbent capacity of the absorbent core may varyto accommodate wearers ranging from infants through adults.

In some embodiments, the diaper has an hour-glass shaped absorbent core.The absorbent core is may be an absorbent member comprising a web orbatt of airfelt, wood pulp fibers, and/or a particulate absorbentpolymeric composition disposed therein.

In some embodiments, the absorbent polymeric composition of theabsorbent core comprises a thermoplastic polymer composition of thepresent invention.

Other non-limiting examples of absorbent articles according to thepresent invention are sanitary napkins designed to receive and containvaginal discharges such as menses. Disposable sanitary napkins aredesigned to be held adjacent to the human body through the agency of agarment, such as an undergarment or a panty or by a specially designedbelt. Examples of the kinds of sanitary napkins to which the presentinvention is readily adapted are shown in U.S. Pat. No. 4,687,478 and inU.S. Pat. No. 4,589,876. It will be apparent that the films of thepresent invention comprising a thermoplastic polymer composition of thepresent invention described herein may be used as the liquid imperviousbacksheet of such sanitary napkins. On the other hand it will beunderstood the present invention is not limited to any specific sanitarynapkin configuration or structure.

In general, sanitary napkins comprise a liquid impervious backsheet, aliquid pervious topsheet, and an absorbent core placed between thebacksheet and the topsheet. The backsheet comprises a thermoplasticpolymer composition of the present invention. The topsheet may compriseany of the topsheet materials discussed with respect to diapers. Theadhesives used in may also comprise a thermoplastic polymer compositionof the present invention. The absorbent core may comprise any of theabsorbent core materials discussed with respect to diapers, including athermoplastic polymer composition of the present invention.

Importantly, the absorbent articles according to the present inventionmay be biodegradable and/or compostable to a greater extent thanconventional absorbent articles which employ materials such as apolyolefin (e.g., a polyethylene backsheet).

EXAMPLES Example 1 A Single Layer Film

The following materials are mixed in a Haake Rheocord 90 melt mixer,Thermo Electron Corporation, Newington, N.H.:

30 g Ethylex™ 2015, hydroxyethylated starch (Tate and Lyle, Decatur,Ill.)12.5 g Glycerol (Aldrich Chemicals, St. Louis, Mo.)7.5 g Adipic Acid (Aldrich Chemicals, St. Louis, Mo.)

The starch and the glycerol are mixed for about 3 minutes at about 60rpm at a temperature of about 160° C. The balance of components areadded and mixed for an additional 7 minutes at about 60 rpm. Thecontents are removed and allowed to cool to room temperature. Themixture is then chopped using a knife into pieces approximately 50 mm indiameter.

After 24 hours, films of starch composition are made by melting thematerial between Teflon sheets in a Carver™ Press (Fred S. Carver Inc.,Menomonee Falls, Wis.) at 165° C. Pressure on the sheets are adjusted toproduce films of approximately 0.25 mm thick. The films are thenidentically cooled to room temperature by placing the molds betweenlarge (5 kg) aluminum plates and allowing the films to cool to roomtemperature.

One film is dried in a vacuum oven at 90° C. and 30 mm Hg for 12 hours.One film is dried in a convection oven at 115° C. for 12 hours. Anotherfilm simply allowed to cool for 12 hours at ambient air temperature(about 22° C.). The respective films are subjected to the waterstability test as described herein. The films which were dried atelevated temperature (90° C. and 115° C.) do not dissolve or break-up,displaying water stability as defined herein. Films that are allowedsimply to cool, without heat treatment, break up completely after 24hours in water.

Example 2 Comparative Example

This example demonstrates a conventional process for melt mixing andcreating films which are not water stable. The following materials aremixed in the described Haake Rheocord 90 melt mixer:

30 g Ethylex™ 2015 starch (Tate and Lyle, Decatur, Ill.)12.5 g Glycerol (Aldrich Chemicals, St. Louis, Mo.)

The starch and the glycerol are mixed for about 3 minutes at about 60rpm at a temperature of about 160° C. The balance of components areadded and mixed for an additional 7 minutes at about 60 rpm. Thecontents are removed and allowed to cool to room temperature. Themixture is then chopped using a knife into pieces approximately 50 mm indiameter.

After 24 hours, films of starch composition are made by melting thematerial between Teflon sheets in a Carver™ Press (Fred S. Carver Inc.,Menomonee Falls, Wis.) at 165° C. Pressure on the sheets are adjusted toproduce films of approximately 0.25 mm thick. The films are thenidentically cooled to room temperature by placing the molds betweenlarge (5 kg) aluminum plates and allowing the films to cool to roomtemperature.

One film is dried in a vacuum oven at 90° C. and 30 mm Hg for 12 hours.One film is dried in a convection oven at 115° C. for 12 hours. Anotherfilm simply allowed to cool for 12 hours at ambient air temperature(about 22° C.). The respective films are subjected to the waterstability test as described herein. In this case the films which weredried at elevated temperature (90° C. and 115° C.) and ambienttemperature, break up completely after 24 hours in water and fail thewater stability.

Example 3 Single Layer Film

This example demonstrates additional blending of TPS with waterstability. The following materials are used:

6000 g Ethylex™ 2035 (Tate & Lyle, Decatur, Ill.)

2500 g Glycerol (Aldrich Chemicals, St. Louis, Mo.)350 g Adipic acid (Solutia Chemicals, St. Louis, Mo.)

500 g Polypropylene Profax™ PH835(Basell, Elkton, Md.)

500 g Maleated polypropylene G3003 (Eastman Chemicals, Kingsport, Tenn.)50 g Magnesium stearate (Aldrich Chemicals, St. Louis, Mo.)

The starch, adipic acid, polypropylene, maleated polypropylene andmagnesium stearate (employed as a process aid) are dry mixed in aHenschel Raw Material Mixer (Green Bay, Wis.) for 4 minutes at 1000 rpm.The mixture is then fed into a B&P Process System Twin Screw ExtrusionCompounding System (Saginaw, Mich.) with 40 mm co-rotating screws.Glycerol is fed through a liquid feed port at a rate that maintains thedesired composition stated above. The screw speed is set at 90 rpm withthe thermal profile as shown below:

Temperature zone 1 zone 2 zone 3 zone 4 zone 5 zone 6 zone 7 zone 8 zone9 die Set (° C.) 85 85 100 145 155 160 160 160 140 100 Actual (° C.) 8383 85 138 138 144 155 147 133 98At these conditions the overall extrusion rate is 20 lbs/hour. A vacuumline is applied to two of three vent ports to extract water from thematerial during pelletization. Torque is 10%. The mixture is extrudedinto strands 0.3-0.8 cm in diameter and the strands are chopped to formpellets via a Conair pellitizer. The pellets are fed into a single screwextruder (Rheomix Model 202) with screw diameter of 0.75 inch. Aconstant taper screw having 20:1 length to diameter ratio and a 3:1compression ratio is employed. The temperature of both heating zones ofthe extruder barrel is 160° C. The extruder is equipped with a die ofwidth 6 inch and a die gap of 0.04 inch. The die is maintained at 100°.The screw rpm is kept constant at 30 rpm. The composition is forcedthrough the die and is collected on a take-up roll collection system(Postex) at a rate that allows solidification of the Thermoplasticstarch before take-up. The width of these films are nominally 4 inch andthe thickness are approximately 0.002 inch.

After cooling to room temperature for 24 hours, 100 cm of film is driedin a vacuum oven at 90° C. and 30 mm Hg for 12 hours. Another 100 cm offilm is dried in a convection oven at 115° C. for 12 hours. Another 100cm of film is simply allowed to cool for 12 hours at ambient airtemperature (about 22° C.). The respective films are subjected to thewater stability test as described herein. The films which were dried atelevated temperature (90° C. and 115° C.) do not dissolve or break-up,displaying water stability as defined herein. Films that are allowedsimply to cool, without heat treatment, break up completely after 24hours in water.

Example 4 A Single Layer Film

The following materials are mixed in a Haake Rheocord 90 melt mixer,Thermo Electron Corporation, Newington, N.H.:

30 g Ethylex™ 2035 (Tate& Lyle, Decatur, Ill.)

12.5 g Glycerol (Aldrich Chemicals, St. Louis, Mo.)1.7 g Adipic acid (Solutia Chemicals, St. Louis, Mo.)

2.5 g Polypropylene PH835 (Basell, Elkton, Md.))

2.5 g Maleated polypropylene G3003 (Eastman Chemicals, Kingsport, Tenn.)0.25 g Magnesium stearate (Aldrich Chemicals, St. Louis, Mo.)

The starch and the glycerol are mixed for about 3 minutes at about 60rpm at a temperature of about 165° C. The balance of components areadded and mixed for an additional 7 minutes at about 60 rpm. Thecontents are removed and allowed to cool to room temperature. Themixture is then chopped using a knife into pieces approximately 50 mm indiameter.

After 24 hours, films of starch composition are made by melting thematerial between Teflon sheets in a Carver™ Press (Fred S. Carver Inc.,Menomonee Falls, Wis.) at 165° C. Pressure on the sheets are adjusted toproduce films of approximately 0.25 mm thick. The films are thenidentically cooled to room temperature by placing the molds betweenlarge (5 kg) aluminum plates and allowing the films to cool to roomtemperature.

One film is dried in a vacuum oven at 90° C. and 30 mm Hg for 12 hours.One film is dried in a convection oven at 115° C. for 12 hours. Anotherfilm simply allowed to cool for 12 hours at ambient air temperature(about 22° C.). The respective films are subjected to the waterstability test as described herein. The films which were dried atelevated temperature (90° C. and 115° C.) do not dissolve or break-up,displaying water stability as defined herein. Films that are allowedsimply to cool, without heat treatment, break up completely after 24hours in water.

Example 5 A Single Layer Film

The following materials are mixed in a Haake Rheocord 90 melt mixer,Thermo Electron Corporation, Newington, N.H.:

30 g Ethylex™ 2035 (Tate& Lyle, Decatur, Ill.)

12.5 g Glycerol (Aldrich Chemicals, St. Louis, Mo.)2.5 g Adipic acid (Solutia Chemicals, St. Louis, Mo.)5.0 g Maleated polypropylene G3003 (Eastman Chemicals, Kingsport, Tenn.)0.25 g Magnesium stearate (Aldrich Chemicals, St. Louis, Mo.)

The starch and the glycerol are mixed for about 3 minutes at about 60rpm at a temperature of about 165° C. The balance of components areadded and mixed for an additional 7 minutes at about 60 rpm. Thecontents are removed and allowed to cool to room temperature. Themixture is then chopped using a knife into pieces approximately 50 mm indiameter.

After 24 hours, films of starch composition are made by melting thematerial between Teflon sheets in a Carver™ Press (Fred S. Carver Inc.,Menomonee Falls, Wis.) at 165° C. Pressure on the sheets is adjusted toproduce films of approximately 0.25 mm thick. The films are thenidentically cooled to room temperature by placing the molds betweenlarge (5 kg) aluminum plates and allowing the films to cool to roomtemperature.

One film is dried in a vacuum oven at 90° C. and 30 mm Hg for 12 hours.One film is dried in a convection oven at 115° C. for 12 hours. Anotherfilm simply allowed to cool for 12 hours at ambient air temperature(about 22° C.). The respective films are subjected to the waterstability test as described herein. The films which were dried atelevated temperature (90° C. and 115° C.) do not dissolve or break-up,displaying water stability as defined herein. Films that are allowedsimply to cool, without heat treatment, break up completely after 24hours in water.

Example 6 Multilayer Laminate Film

A sheet of thermoplastic starch film may be prepared as in Example 5except for the final step of drying in a vacuum oven. The thermoplasticsheet may then be encased by a sheets of a polymer with better waterbarrier properties such as polypropylene. This may be the case when evengreater water barrier properties are needed. The films are placed inCarver™ press stacked in the following order polypropylene (BasellProfax™ PH835), Thermoplastic starch, polypropylene. The material isthen pressed at a temperature 160° C. After compression at 2000 lb for10 min, the pressure is released and the film is allowed to cool to roomtemperature. The assembly is dried in a vacuum oven at 115° C. for 12hours as in example 1.

Example 7 Disposable Diaper

A disposable baby diaper according to this invention is prepared asfollows. The dimensions listed are for a diaper intended for use with achild in the 6-10 kilogram size range. These dimensions can be modifiedproportionately for different size children, or for adult incontinencebriefs, according to standard practice.

1. Backsheet: 0.020-0.038 mm film consisting of a Thermoplastic starch(prepared as described in Example 3); width at top and bottom 33 cm;notched inwardly on both sides to a width-at-center of 28.5 cm; length50.2 cm.

2. Topsheet: carded and thermally bonded staple-length polypropylenefibers (Hercules type 151 polypropylene); width at top and bottom 33 cm;notched inwardly on both sides to a width-at-center of 28.5 cm; length50.2 cm.

3. Absorbent core: comprises 28.6 g of cellulose wood pulp and 4.9 g ofabsorbent gelling material particles (commercial polyacrylate fromNippon Shokubai); 8.4 mm thick, calendered; width at top and bottom 28.6cm; notched inwardly at both sides to a width-at-center of 10.2 cm;length 44.5 cm.

4. Elastic leg bands: four individual rubber strips (2 per side); width4.77 mm; length 370 mm; thickness 0.178 mm (all the foregoing dimensionsbeing in the relaxed state).

The diaper is prepared in standard fashion by positioning the corematerial covered with the topsheet on the backsheet and gluing.

The elastic bands (designated “inner” and “outer”, corresponding to thebands closest to, and farthest from, the core, respectively) arestretched to ca. 50.2 cm and positioned between the topsheet/backsheetalong each longitudinal side (2 bands per side) of the core. The innerbands along each side are positioned ca. 55 mm from the narrowest widthof the core (measured from the inner edge of the elastic bank). Thisprovides a spacing element along each side of the diaper comprising theflexible topsheet/backsheet material between the inner elastic and thecurved edge of the core. The inner bands are glued down along theirlength in the stretched state. The outer bands are positioned ca. 13 mmfrom the inner bands, and are glued down along their length in thestretched state. The topsheet/backsheet assembly is flexible, and theglued-down bands contract to elasticize the sides of the diaper.

Example 8 Lightweight Pantiliner

A lightweight pantiliner suitable for use between menstrual periodscomprises a pad (surface area 117 cm²; SSK air felt 3.0 g) containing1.0 g of absorbent gelling material particles (commercial polyacrylate;Nippon Shokubai); said pad being interposed between a porous formed-filmtopsheet according to U.S. Pat. No. 4,463,045 and a backsheet whichcomprises a 0.03 mm thickness thermoplastic starch film, as prepared inaccordance with Example 3.

Example 9 Sanitary Napkin

A catamenial product in the form of a sanitary napkin having two flapsextending outward from its absorbent core is prepared using a pad in themanner of Example 8 (surface area 117 cm²; 8.5 g SSK air felt), per thedesign of U.S. Pat. No. 4,687,478, Van Tillburg, Aug. 18, 1987. Thebacksheet and topsheet materials are the same as described in Example 8.

Example 10 Single Layer Film

This example demonstrates additional blending of TPS with waterstability. The following materials are used:

6000 g Ethylex™ 2025 (Tate& Lyle, Decatur, Ill.)

2300 g Glycerol (Aldrich Chemicals, St. Louis, Mo.)350 g Adipic acid (Solutia Chemicals, St. Louis, Mo.)

500 g Polypropylene Profax™ PH 835 (Basell, Elkton, Md.)

500 g Maleated polypropylene G3003 (Eastman Chemicals, Kingsport, Tenn.)50 g Magnesium stearate (Aldrich Chemicals, St. Louis, Mo.)

The starch, adipic acid, polypropylene, maleated polypropylene andmagnesium stearate (employed as a process aid) are dry mixed in aHenschel Raw Material Mixer (Green Bay, Wis.) for 4 minutes at 1000 rpm.The mixture is then fed into a B&P Process System Twin Screw ExtrusionCompounding System (Saginaw, Mich.) with 40 mm co-rotating screws.Glycerol is fed through a liquid feed port at a rate that maintains thedesired composition stated above. The screw speed is set at 90 rpm withthe thermal profile as shown below:

Temperature zone 1 zone 2 zone 3 zone 4 zone 5 zone 6 zone 7 zone 8 zone9 die Set (° C.) 85 85 100 145 155 160 160 160 140 100 Actual (° C.) 8383 85 138 138 144 155 147 133 98At these conditions the overall extrusion rate is 20 lbs/hour. A vacuumline is applied to two of three vent ports to extract water from thematerial during pelletization. Torque is 10%. The mixture is extrudedinto strands 0.3-0.8 cm in diameter and the strands are chopped to formpellets via a Conair pellitizer. The pellets are fed into a single screwextruder (Rheomix Model 202) with screw diameter of 0.75 inch. Aconstant taper screw having 20:1 length to diameter ratio and a 3:1compression ratio is employed. The temperature of both heating zones ofthe extruder barrel is 160° C. The extruder is equipped with a die ofwidth 6 inch and a die gap of 0.04 inch. The die is maintained at 100°.The screw rpm is kept constant at 30 rpm. The composition is forcedthrough the die and is collected on a take-up roll collection system(Postex) at a rate that allows solidification of the Thermoplasticstarch before take-up. The width of these films are nominally 4 inch andthe thickness are approximately 0.002 inch.After cooling to room temperature for 24 hours, 100 cm of film is driedin a vacuum oven at 90° C. and 30 mm Hg for 12 hours. Another 100 cm offilm is dried in a convection oven at 115° C. for 12 hours. Another 100cm of film is simply allowed to cool for 12 hours at ambient airtemperature (about 22° C.). The respective films are subjected to thewater stability test as described herein. The films which were dried atelevated temperature (90° C. and 115° C.) do not dissolve or break-up,displaying water stability as defined herein. Films that are allowedsimply to cool, without heat treatment, break up completely after 24hours in water.

Example 11 Disposable Diaper

The diaper of Example 7 is modified by replacing the backsheet with abacksheet consisting of a 0.020 to 0.038 mm thickness film comprising astarch thermoplastic film prepared as described in Example 10.

Example 12 Sheet

The film preparation procedure of Example 3 is modified by replacing thedie on the extruder with a slot die of thickness approximately 0.25 cmand width 15 cm. Take-up after extrusion is accomplished by insertingthe sheet emerging from the extruder between two counter-rotatingcylinders. The sheet is drawn from the extruder in this manner and cutin lengths of 32 cm. Sheets of approximately 13 cm wide and 0.18 cmthick are obtained.

Example 13 Rigid Foam

A thermoplastic starch composition is prepared as in example 5, and 30 gof the thermoplastic starch composition and 0.3 g, Celogen® 125 FF(Chemtura Corporation, Middlebury, Conn.), a modified azodicarbonamideare charged to the mixing chamber of a Rheomix type 600 melt blenderequipped with roller blades. The mixing chamber temperature is heatedabove the melting temperature of thermoplastic starch (165° C.), butbelow the degradation temperature of the blowing agent (195° C.). Aftermixing for 10 minutes at 60 rpm, the mixture is collected and istransferred to a heated aluminum pan, spread about so that the resultingmass is about 0.5 cm in thickness. The mixture is then place in an oven(National Appliance Company, model 5830) and heated to the TPS melttemperature again (165° C.), and is held at that temperature until thethermoplastic starch composition is completely molten (ca. 5 min). Theoven temperature is then raised to 200° C. at which temperature theblowing agent degrades and thermoplastic composition begins foaming. Atthis point the thermoplastic starch foam is removed from the 200° C.oven. After cooling to room temperature the thermoplastic starch foam isplaced in a oven at 115° C. for 12 hours.

Example 14 Molded Article

Injection molded articles are obtained by using a Mini Max Molder™ modelCS-183 (Custom Scientific Instruments, Whippeny, N.J.). The temperatureof the rotor and strator cup is held constant at 165° C. About 1.0 gramsthe thermoplastic starch pellets as described in example 10 is chargedto the stator cup and allowed to melt for 3 minutes. The moltenthermoplastic starch composition is radially mixed by raising andlowering the rotor tip five times. A dumbbell-shaped steel mold issprayed with a light coating of mold silicone release agent. The mold isplaced on the mold support wheel of the Mini Max Molder™ and the moltencomposition is injected into the mold by action of the rotor tip. Thethermoplastic starch is molded into a dumbbell shaped pieces 0.03 inchthick, 1 inch long, 0.125 inch wide at the middle of the piece and 0.25inch wide at the ends. These molded parts are suitable for mechanicaltesting. The test pieces are placed in a vacuum oven at 115° C. for 12hours. They are then subjected to a water stability test where they areplaced in 1000 ml of tap water for 24 hours, then removed from the waterand allowed to dry for 24 hours. They experience less than 10%dimensional change from their pre-soak dimensions and are said to havepassed the water stability test.

Example 15 Compostable Adhesive

Thermoplastic starch compositions described herein may be used as ahot-melt adhesive. A composition of thermoplastic starch is prepared asin example 10, except that instead of casting the pellets into a film,they will be used as an adhesive in the following manner. About 1 g ofthe thermoplastic starch is placed between two sheets of paper (GeorgiaPacific Spectrum DP white), The assembly is placed in a Carver™ Press(Fred S. Carver Inc., Menomonee Falls, Wis.) and is then pressed at atemperature 165° C. After compression at 2000 lb force for 30 min, thepressure is released and the bonded assembly is allowed to cool to roomtemperature.

Example 16 Coating on Fabric

A film of is prepared as described in example 5 except for the finaldrying step in a vacuum oven. The Thermoplastic starch sheet is placedon top of a 5 inch square section of untreated cotton fabric. Theassembly is placed between release paper (Idesco) and placed into aCarver™ Press preheated to 160° C. The fabric/TPS assembly is pressedfor 20 seconds at 1000 lbs. The resulting coated fabric is then removedfrom the press and allowed to cool. The coated fabric is then placed ina vacuum oven and dried at 115° C. for 12 hours then removed and allowedto cool. The fabric is then subjected to the following test to checkwater stability. About 20 ml of tap water is placed on the thermoplasticcoated side of the fabric and allowed to remain for 1 hour. The fabricis free of darkening that would indicate penetration of the water.

Example 17 Binder Fibers

This example demonstrates additional blending and spinning of binderfibers with water stability. The following materials are used:

6000 g Ethylex™ 2015 (Tate & Lyle, Decatur, Ill.)

2500 g Glycerol (Aldrich Chemicals, St. Louis, Mo.)350 g Adipic acid (Solutia Chemicals, St. Louis, Mo.)500 g Maleated polypropylene (Eastman Chemicals, Kingsport, Tenn.)50 g Magnesium stearate (Aldrich Chemicals, St. Louis, Mo.)

The starch, adipic acid, maleated polypropylene and magnesium stearateare dry mixed in a Henschel Raw Material Mixer (Green Bay, Wis.) for 4minutes at 1000 rpm. The mixture is then fed into a B&P Process SystemTwin Screw Extrusion Compounding System (Saginaw, Mich.) with 40 mmco-rotating screws. Glycerol is fed through a liquid feed port at a ratethat maintains the desired composition (stated above). The screw speedis set at 90 rpm with the thermal profile as shown below:

Temperature zone 1 zone 2 zone 3 zone 4 zone 5 zone 6 zone 7 zone 8 zone9 die Set (° C.) 85 85 100 145 155 160 160 160 140 100 Actual (° C.) 8383 85 138 138 144 155 147 133 98

At these conditions the overall extrusion rate is 20 lbs/hour. A vacuumline is applied to two of three vent ports to extract water from thematerial during pelletization. Torque is 10%. The mixture is extrudedinto strands 0.3-0.8 cm in diameter and the strands are chopped to formpellets via a Conair pellitizer. The pellets are dried for 12 hours in athrough air dryer at 150° F. The pellets are fed into a Hills 4-holeextruder test stand (Hills, Inc., West Melbourne, Fla.) with a Hillsbicomponent sheath/core 4-hole spin pack. The equipment features twoextruders that feed to a single spin head to produce bicomponent fibers.For single component fibers, both extruders are set to identicalconditions as follows and the same material is fed into both extruders:

Extruder Melt Melt Barrel Barrel Barrel Extruder Pump Spin Pressure Zone1 Zone 2 Zone 3 Pressure Speed Head (psi) (° C.) (° C.) (° C.) (psi)(rpm) (° C.) Set 1400 125 160 170 1500 464 165 Extruder 1 (° C.) Set1400 125 160 170 1500 464 Extruder 2 (° C.)Fibers are collected in on a screen through an attenuating air jet at amass throughput of 0.8 g/hole-min. The air jet is set at 20 psi. TheThermoplastic starch fibers are collected, chopped with a knife tolengths approximately 2 cm. The starch fibers are mixed with unbondedstaple polyester fibers (Wellman, Fort Mill, S.C.) at a ratio of 10:1 byweight polyester to starch web for a total basis weight of approximately50 gsm. The unbonded web is placed in a Carver™ press and pressed at1000 psi at 165° C. for 10 minutes between Teflon sheets. The web isremoved and allowed to cool. The web is dried overnight in a vacuum ovenat 115° C. The web is subjected to the following water stability test: A5 cm×5 cm web is placed in 1000 ml of water and allowed to soak for 24hours. The web is removed and if it remains intact, it is said to passthe water stability test. The dried web passes the water stability test.

Example 18 A Single Layer Film

The following materials are mixed in a Haake Rheocord 90 melt mixer,Thermo Electron Corporation, Newington, N.H.:

30 g Ethylex™ 2035 (Tate & Lyle, Decatur, Ill.)

12.5 g Glycerol (Aldrich Chemicals, St. Louis, Mo.)2.5 g Adipic acid (Solutia Chemicals, St. Louis, Mo.)2.5 g Soybean oil (Aldrich Chemicals, St. Louis, Mo.)5.0 g Maleated polypropylene G3003 (Eastman Chemicals, Kingsport, Tenn.)0.25 g Magnesium stearate (Aldrich Chemicals, St. Louis, Mo.)

The starch and the glycerol are mixed for about 3 minutes at about 60rpm at a temperature of about 165° C. The balance of components areadded and mixed for an additional 7 minutes at about 60 rpm. Thecontents are removed and allowed to cool to room temperature. Themixture is then chopped using a knife into pieces approximately 50 mm indiameter.

After 24 hours, films of starch composition are made by melting thematerial between Teflon sheets in a Carver™ Press (Fred S. Carver Inc.,Menomonee Falls, Wis.) at 165° C. Pressure on the sheets are adjusted toproduce films of approximately 0.25 mm thick. The films are thenidentically cooled to room temperature by placing the molds betweenlarge (5 kg) aluminum plates and allowing the films to cool to roomtemperature.

One film is dried in a vacuum oven at 90° C. and 30 mm Hg for 12 hours.One film is dried in a convection oven at 115° C. for 12 hours. Anotherfilm simply allowed to cool for 12 hours at ambient air temperature(about 22° C.). The respective films are subjected to the waterstability test as described herein. The films which were dried atelevated temperature (90° C. and 115° C.) do not dissolve or break-up,displaying water stability as defined herein. Films that are allowedsimply to cool, without heat treatment, break up completely after 24hours in water.

Example 19 A Single Layer Film

The following materials are mixed in a Haake Rheocord 90 melt mixer,Thermo Electron Corporation, Newington, N.H.:

30 g Ethylex™ 2035 (Tate& Lyle, Decatur, Ill.)

12.5 g Glycerol (Aldrich Chemicals, St. Louis, Mo.)2.5 g Adipic acid (Solutia Chemicals, St. Louis, Mo.)2.5 g Linseed oil (Aldrich Chemicals, St. Louis, Mo.)5.0 g Maleated polypropylene G3003 (Eastman Chemicals, Kingsport, Tenn.)0.25 g Magnesium stearate (Aldrich Chemicals, St. Louis, Mo.)

The starch and the glycerol are mixed for about 3 minutes at about 60rpm at a temperature of about 165° C. The balance of components areadded and mixed for an additional 7 minutes at about 60 rpm. Thecontents are removed and allowed to cool to room temperature. Themixture is then chopped using a knife into pieces approximately 50 mm indiameter.

After 24 hours, films of starch composition are made by melting thematerial between Teflon sheets in a Carver™ Press (Fred S. Carver Inc.,Menomonee Falls, Wis.) at 165° C. Pressure on the sheets are adjusted toproduce films of approximately 0.25 mm thick. The films are thenidentically cooled to room temperature by placing the molds betweenlarge (5 kg) aluminum plates and allowing the films to cool to roomtemperature.

One film is dried in a vacuum oven at 90° C. and 30 mm Hg for 12 hours.One film is dried in a convection oven at 115° C. for 12 hours. Anotherfilm simply allowed to cool for 12 hours at ambient air temperature(about 22° C.). The respective films are subjected to the waterstability test as described herein. The films which were dried atelevated temperature (90° C. and 115° C.) do not dissolve or break-up,displaying water stability as defined herein. Films that are allowedsimply to cool, without heat treatment, break up completely after 24hours in water.

Example 20 A Single Layer Film

The following materials are mixed in a Haake Rheocord 90 melt mixer,Thermo Electron Corporation, Newington, N.H.:

30 g Ethylex™ 2035 (Tate& Lyle, Decatur, Ill.)

12.5 g Glycerol (Aldrich Chemicals, St. Louis, Mo.)2.5 g Adipic acid (Solutia Chemicals, St. Louis, Mo.)5.0 g Maleated polypropylene G3003 (Eastman Chemicals, Kingsport, Tenn.)0.0125 g p-Toluenesulfonic acid (Aldrich Chemicals, St. Louis, Mo.)0.25 g Magnesium stearate (Aldrich Chemicals, St. Louis, Mo.)

The starch and the glycerol are mixed for about 3 minutes at about 60rpm at a temperature of about 165° C. The balance of components areadded and mixed for an additional 7 minutes at about 60 rpm. Thecontents are removed and allowed to cool to room temperature. Themixture is then chopped using a knife into pieces approximately 50 mm indiameter.

After 24 hours, films of starch composition are made by melting thematerial between Teflon sheets in a Carver™ Press (Fred S. Carver Inc.,Menomonee Falls, Wis.) at 165° C. Pressure on the sheets are adjusted toproduce films of approximately 0.25 mm thick. The films are thenidentically cooled to room temperature by placing the molds betweenlarge (5 kg) aluminum plates and allowing the films to cool to roomtemperature.

One film is dried in a vacuum oven at 90° C. and 30 mm Hg for 12 hours.One film is dried in a convection oven at 115° C. for 12 hours. Anotherfilm simply allowed to cool for 12 hours at ambient air temperature(about 22° C.). The respective films are subjected to the waterstability test as described herein. The films which were dried atelevated temperature (90° C. and 115° C.) do not dissolve or break-up,displaying water stability as defined herein. Films that are allowedsimply to cool, without heat treatment, break up completely after 24hours in water.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm”

All documents cited in the Detailed Description of the Invention are, inrelevant part, incorporated herein by reference; the citation of anydocument is not to be construed as an admission that it is prior artwith respect to the present invention. To the extent that any meaning ordefinition of a term in this written document conflicts with any meaningor definition of the term in a document incorporated by reference, themeaning or definition assigned to the term in this written documentshall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

1. A thermoplastic polymer composition comprising a blend of: a. fromabout 50% to about 85% of destructured starch; and b. from about 5% toabout 50% of either transesterification products or a combination ofester condensation products and transesterification products; whereinsaid ester condensation products are formed in situ during the blendingof said destructured starch with a reactant mixture comprising: i.polyhydric alcohol having alcohol functional groups; ii. triglyceride;and iii. acid wherein said thermoplastic polymer composition is WaterStable.
 2. The thermoplastic polymer composition of claim 1, whereinsaid polyhydric alcohol is selected from the group consisting of:glycerol; glycol; sugar; sugar alcohol; and combinations thereof. 3.(canceled)
 4. The thermoplastic polymer composition of claim 1, whereinsaid polymer composition is blended with additional polymer.
 5. Thethermoplastic polymer composition of claim 4, wherein said additionalpolymer is selected from the group consisting of: polyhydroxyalkanoate;polyvinyl alcohol; polyethylene; polypropylene; polyethyleneterephthalate; maleated polyethylene; maleated polypropylene; polylacticacid; modified polypropylene; nylon; caprolactone; and combinationsthereof.
 6. The thermoplastic polymer composition of claim 1, whereinsaid composition is combined with filler to form a composite.
 7. Thethermoplastic polymer composition of claim 6, wherein said filler isselected from the group consisting of: talc; clay; pulp; flour; walnutshells; cellulose; cotton; jute; raffia; rice chaff; animal bristles;chitin; granular starch; diatomaceous earth; nanoparticles; carbonfibers; kenaf; and combinations thereof.
 8. A plastic article comprisingthe thermoplastic polymer composition according to claim
 1. 9. Theplastic article of claim 8, wherein said article is a molded article,extruded article, and combinations thereof.
 10. The plastic article ofclaim 9, wherein said article is selected from the group consisting of:sheets; films; adhesives; binders; laminates; coatings; foams; andcombinations thereof.
 11. A personal hygiene article comprising thethermoplastic polymer composition according to claim
 1. 12. An absorbentarticle comprising the thermoplastic polymer composition according toclaim
 1. 13. Packaging comprising the thermoplastic polymer compositionaccording to claim
 1. 14. The thermoplastic polymer composition of claim1, wherein said composition is biodegradable.
 15. The thermoplasticpolymer composition of claim 14, further comprising polymers selectedfrom the group consisting of: polyvinyl alcohol; ester polycondensates;aliphatic/aromatic polyesters; and combinations thereof.
 16. Thethermoplastic polymer composition of claim 15, wherein said polymers areselected from the group consisting of: polybutylene succinate;polybutylene succinate co-adipate; co-polyesters of butylene diol,adipic acid, terephtalic acid, and combinations thereof; andcombinations thereof.
 17. A thermoplastic starch composition comprisinga mixture of: a. from about 50% to about 85%, by weight of thecomposition mixture, of starch selected from the group consisting ofnative starch, destructured starch, and combinations thereof; b. fromabout 11% to about 50%, by weight of the composition mixture, of eithertransesterification products or a combination of ester condensationproducts and transesterification products formed in situ from a reactantmixture comprising, by weight of the composition mixture: i. from about10% to about 30% polyhydric alcohol; ii. from about 1% to about 20% of atriglyceride compound; and iii. from about 0.1% to about 30% of an acid;wherein the amount of polyhydric alcohol is reduced to effect waterstability of the thermoplastic starch composition. c.
 18. Thethermoplastic starch composition of claim 17, wherein said starch isdestructured starch.
 19. (canceled)
 20. (canceled)
 21. (canceled) 22.(canceled)
 23. (canceled)
 24. A thermoplastic polymer compositioncomprising a water stabilized blend of: a. from about 50% to about 85%of thermoplastic destructured starch; and b. from about 5% to about 50%of reaction products formed in situ during the blending of saidthermoplastic destructured starch with a reactant mixture comprising: i.polyhydric alcohol; and ii. a triglyceride compound, wherein saidreaction product is formed from a transesterification reaction; andwherein the amount of polyhydric alcohol is reduced to effect waterstability of the thermoplastic polymer composition.
 25. (canceled) 26.(canceled)